CN1073435A - Use γ, δ-epoxy butylene produces 2, the continuous processing of 5-dihydrofuran - Google Patents

Use γ, δ-epoxy butylene produces 2, the continuous processing of 5-dihydrofuran Download PDF

Info

Publication number
CN1073435A
CN1073435A CN92114824.0A CN92114824A CN1073435A CN 1073435 A CN1073435 A CN 1073435A CN 92114824 A CN92114824 A CN 92114824A CN 1073435 A CN1073435 A CN 1073435A
Authority
CN
China
Prior art keywords
reaction zone
iodate
substituting group
dihydrofuran
compound
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN92114824.0A
Other languages
Chinese (zh)
Other versions
CN1050837C (en
Inventor
G·W·菲利普斯
S·N·法林
S·A·戈列斯基
J·R·蒙尼埃
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Eastman Kodak Co
Original Assignee
Eastman Kodak Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Eastman Kodak Co filed Critical Eastman Kodak Co
Publication of CN1073435A publication Critical patent/CN1073435A/en
Application granted granted Critical
Publication of CN1050837C publication Critical patent/CN1050837C/en
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
    • C07D307/26—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
    • C07D307/28—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/06—Halogens; Compounds thereof
    • B01J27/08—Halides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
    • B01J31/0235—Nitrogen containing compounds
    • B01J31/0239—Quaternary ammonium compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
    • B01J31/0255—Phosphorus containing compounds
    • B01J31/0267—Phosphines or phosphonium compounds, i.e. phosphorus bonded to at least one carbon atom, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, the other atoms bonded to phosphorus being either carbon or hydrogen
    • B01J31/0268—Phosphonium compounds, i.e. phosphine with an additional hydrogen or carbon atom bonded to phosphorous so as to result in a formal positive charge on phosphorous
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
    • B01J31/122—Metal aryl or alkyl compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/50—Redistribution or isomerisation reactions of C-C, C=C or C-C triple bonds
    • B01J2231/52—Isomerisation reactions

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
  • Catalysts (AREA)
  • Saccharide Compounds (AREA)
  • Epoxy Resins (AREA)
  • Epoxy Compounds (AREA)

Abstract

The invention discloses and containing iodate  compound and lewis acidic catalyst system and containing 2,5-dihydrofuran product and γ, the process solvent of the mixture of δ-epoxy olefin reactant oligopolymer exists down, in liquid phase by making γ, the method of δ-epoxy isomerisation of olefin processes 2, the continuous processing of 5-dihydrofuran.

Description

Use γ, δ-epoxy butylene produces 2, the continuous processing of 5-dihydrofuran
The present invention relates in liquid phase, use isomerization γ, δ-epoxy olefin processes processing 2, the continuous processing of 5-dihydrofuran.Especially the present invention relates at the catalyst system that contains iodinated compounds and Lewis acid and contain 2 of this technology, 5-dihydrofuran product and γ, the process solvent of the oligopolymer composition of δ-epoxy olefin reactant exists down, makes γ, the method for δ-epoxy continous olefin hydrocarbon isomerization.
U.S.4,897,498 and 4,950,773 have introduced with selectivity monocycle oxidation divinyl preparation 3,4-epoxy-1-butylene.U.S.4,962,210 have introduced 2, the 5-dihydrofuran is hydrogenated to tetrahydrofuran (THF), it be a kind of the preparation polymkeric substance as poly-(tetramethylene ether) ethylene glycol in as the useful compound of chemical process solvent and intermediate.
U.S.3,932,468 and 3,996,248 disclose by make γ with containing the lewis acidic homogeneous catalyst system of hydrogen iodide or hydrogen bromide and transition metal in organic solvent, and δ-ring hydrogen alkene is that the undersaturated and full divinyl monoepoxide that closes is reset production 2, the method for 5-dihydrofuran.This method has a lot of shortcomings, for example uses corrosive hydrogen halide, needs for example N-N-methyl-2-2-pyrrolidone N-of expensive high boiling point tertiary amide solvent, with dissolving transition metal Lewis acid.We have found that, U.S.3,932,468 and 3,996, it is a large amount of 3 that 248 method also makes, and 4-epoxy-1-butylene changes crotonic aldehyde into.
U.S.5,082,956 has introduced containing in the presence of a certain amount of iodinated compounds and alternative inorganic lewis acid and/or the halid catalyst system of a certain amount of organo-metallic, uses isomerization γ, δ-epoxy olefin processes preparation 2, the method for 5-dihydrofuran.The method of the disclosure comprises vapor phase process, and wherein the steam of epoxy olefin reactant is by containing the reaction zone of catalyst system, and this catalyst body is fused salt or the film like that is stated from the nonacid solid support material.This vapor phase process adopts inert thinner such as nitrogen or helium, and the temperature more than the catalyst component fusing point, especially carries out under 130-150 ℃.
At U.S.5, in the scheme of 082,956 disclosed another kind of isomerization method, in liquid phase with above-mentioned catalyst system under the solution of external inert solvent and 100-150 ℃, with γ, δ-epoxy alkene carries out isomerization, generates dihydrofuran.This method use hydrocarbon or halogenated hydrocarbon solvent as
Figure 921148240_IMG16
, pseudocumol or dichlorobenzene, its boiling point is higher than 2,5-dihydrofuran product is so that with distillation method product separation from catalyst solution.
Use resembles the fused salt or the film catalyst that load on the inert carrier needs high relatively processing temperature (more than the catalyzer melting temperature), will increase the formation of by product and the degraded of catalyzer under this temperature.Selection as the compound of catalyzer also is subjected to the restriction of following condition, and promptly they have enough low fusing point so that it is easy to use.Use carried catalyst also to have problems, promptly can not remove nonvolatile oligopolymer byproduct from reaction zone.Use fused salt and so on catalyzer, when removing or adding the part catalyst mixture, can increase the material intractability.The diluent for gases of use inert need separate the dihydrofuran product in inert gas and the gas product stream in the gas phase process.The solution class catalyzer that use is dissolved in the solvent that boiling point is higher than the dihydrofuran product also has some shortcoming, and as introduce annexing ingredient in production system, they must removed with distillation method subsequently.
We have found that, can make things convenient for and prepare 2 economically with continuous processing, the 5-dihydrofuran, wherein having in the presence of the above-mentioned catalyst system, with containing 2, the γ of 5-dihydrofuran product and oligopolymer, the mixture of δ-epoxy olefine reaction is as process solvent, with γ, δ-epoxy alkene carries out isomerization in liquid phase.Therefore, the invention provides comprise following steps be used to process 2, the continuous processing of 5-dihydrofuran:
(1) infeed γ to the reaction zone that contains following solution continuously, δ-epoxy alkene:
(A) catalyst system of catalytic amount comprises (ⅰ) iodate and the Lewis acid, organotin (IV) compound, organo-antimony compound or their mixture that (ⅱ) are selected from inorganic lewis acid; With
(B) process solvent system comprises 2,5-dihydrofuran product and γ, the oligopolymer of δ-epoxy olefin reactant; With
(2) from reaction zone solution, remove continuously and comprise 2, the gas of 5-dihydrofuran product;
Wherein the liquid phase of reaction zone maintains 65-160 ℃, and the concentration of catalyst system is counted 10-95%(weight by the gross weight of reaction zone liquid in the reaction zone liquid).The oligopolymer component of solvent system is the byproduct of isomerization process, γ wherein, and δ-epoxy olefin reactant is through being rearranged into 2, the 5-dihydrofuran.Oligopolymer is low molecular wt polyethers, separates 2 in the isomerization course of processing or with traditional gas/liquid isolation technique from crude product mixture, and during the 5-dihydrofuran product, polyethers is nonvolatile.Polyether oligomers is by γ, and δ-epoxy olefin reactant ring-opening polymerization effect produces, and this is similar with the situation that is formed polyether oligomers and polymkeric substance by oxyethane and propylene oxide.
The advantage that continuous processing disclosed herein had comprises gentle reaction conditions, the product separation of simplification and can remove and add catalyst system.With 2,5-dihydrofuran product and γ, the mixture of δ-epoxy olefin reactant make the inert process solvent can be made to be reflected to be significantly less than under the temperature that adopts in the vapor phase process and carry out, and catalyzer is to use with fused salt or with the carrier film of gaseous carrier in the vapor phase process.Therefore, the formation of the possibility of catalyst deactivation or decomposition and byproduct is reduced in this technology.
γ, δ-epoxy olefin reactant can contain 4-8 carbon atom, and the example of epoxy alkene and oxirane ring olefin reactant comprises the compound of following structural:
Each R wherein 1Be selected from hydrogen and methyl respectively, 2 R 1Substituting group can be represented alkylidene group jointly, and this alkylidene group can form the cycloalkenyl group of 5-8 carbon atom with the carbon atom that connects them.Preferred epoxy olefin reactant comprises following (I) formula compound, wherein maximum four R 1Substituting group is respectively methyl.Be used to implement instantiation compound of the present invention and comprise 3,4-epoxy-3-methyl-1-butene, 3,4-epoxy-2-methyl-1-butene alkene, 2,3-dimethyl-3,4-epoxy-1-butylene, 3,4-epoxy-1-butylene, 2,5-dimethyl-2,4-hexadiene monoepoxide, 3,4-oxirane ring octene etc.The epoxy olefin reactant is 3 preferably, 4-epoxy-1-butylene.
According to our novel process obtain 2, the 5-dihydrofuran compound has structural formula:
Figure 921148240_IMG18
R wherein 1Substituting group is by above-mentioned definition.By in the obtainable compound of the present invention, the most important thing is 2, the 5-dihydrofuran.
The season iodinated compounds of useful as catalysts is known compound and/or is prepared by disclosed method in this novel process.For example, referring to U.S.3,992,432, and be hereby incorporated by reference.Concrete organic season, iodinated compounds comprised quaternary season iodate, and wherein said substituting group is selected from the alkyl of alkyl or replacement.The cycloalkyl of cycloalkyl or replacement.The heteroaryl of heteroaryl or replacement, wherein each said group can interosculate and form ring-type, heterocycle shape, polycyclic or how assorted cyclic structure, iodinated compounds generally should contain at least 6, better at least 12 carbon atoms.
The example of phosphonium iodide catalyst is following various compound:
（Ⅲ）（R 2） 4Y +I -
（Ⅳ）I -（R 2） 3Y +-R 3-Y +x（R 2） 2+xI x，
Figure 921148240_IMG19
Each R wherein 2Respectively be selected from the alkyl or the substituted alkyl part that have until 20 carbon atoms, 5-20 carbon atom cycloalkyl or substituted cycloalkyl, or the aryl of 6-20 carbon atom or substituted aryl, when perhaps Y is P, each R 2Also can be selected from the alkoxyl group until 20 carbon atoms, the cycloalkyloxy of a 5-20 carbon atom, the aryloxy of 6-10 carbon atom or halogen atom;
2 or 3 R 2Substituting group can be represented the bonded alkylene jointly, and as the alkylidene group of 4-6 backbone c atoms or unsaturated group substituted olefine and the unsaturated group as-CH=CHCH=CHCH=and low alkyl group, the Y atom that they and its are connected forms single or many ring;
Each R 3Be selected from alkylene (hydrocarbylene) part or substituted olefine part separately;
X is 0 or 1, and
Y is N, P or As; Condition be season iodinated compounds contain at least 6 carbon atoms.
Above-mentioned substituting group and integral part can have one or more substituting groups, as following various group:
OR 4,
Figure 921148240_IMG20
,-Si(R 4) 3With X each R wherein 4Be selected from hydrogen separately or until the alkyl of 20 carbon atoms, X is a halogen atom.Term " alkylene part " in this employing is meant the alkylene moiety that has until 6 carbon atoms, and arylidene or many arylidene of 6-20 carbon atom.
Preferred phosphonium iodide catalyst is a quaternary ammonium, especially the quaternary phosphonium iodine compound.Concrete ammonium compound comprises iodate 4 penta ammoniums, iodate four own ammoniums, iodate four hot ammoniums, iodate ammonium in four last of the ten Heavenly stems, iodate four-dodecane ammonium, tetrapropylammonium iodide, tetrabutylammonium iodide, iodate N-octyl group quinine two iodate N, N '-dimethyl-N, N '-two hexadecane base piperazines, iodate dimethyl (hexadecane base) (3-pyrrolidyl propyl group) ammonium, two iodate N, N, N, N ', N ', N '-six (dodecyl) octane-1,8-two ammoniums, two iodate N, N, N, N ', N ', N '-six (dodecyl) butane-1,4-two ammoniums, iodate N-octyl group pyrroles or the like.
Concrete phosphorus compound comprises iodate four hot phosphorus, iodate four fourth phosphorus, iodate triphen (hexyl) phosphorus, iodate triphen (octyl group) phosphorus, iodate three benzyls (octyl group) phosphorus, iodate three benzyls (dodecyl) phosphorus, iodate triphen (decyl) phosphorus, iodate triphen (dodecyl) phosphorus, iodate quadruple (2-methyl-propyl) phosphorus, iodate three (2-methyl-propyl) (butyl) phosphorus, iodate four-dodecyl phosphorus, iodate four-hexadecyl phosphorus, iodate trioctylphosphine (octadecyl) phosphorus, iodate triphen (3, the 3-dimethylbutyl) phosphorus, iodate triphen (3-methyl butyl) phosphorus, iodate three (2-methyl butyl) (3-methyl butyl) phosphorus, iodate triphenyl (2-trimethyl silyl ethyl) phosphorus, iodate three (right-chlorophenyl) (dodecyl) phosphorus, iodate hexyl-three (mesityl) phosphorus, iodate four decyls three (2,4, the 6-trimethylammonium) phosphorus, iodate dodecyl three (2,4, the 6-trimethylbenzene) phosphorus or the like.
It is particularly preferred containing the four replacement ammoniums and the phosphorus iodine compound that add up to 16-64 carbon atom.This compounds has structural formula:
Figure 921148240_IMG21
Each R wherein 5Substituting group is selected from the alkyl until 20 carbon atoms separately, each R 6Substituting group is selected from R separately 5, benzyl, phenyl or with 3 phenyl that substituting group replaces at the most, substituting group is selected from low alkyl (until the alkyl of 4 carbon atoms), lower alkoxy or halogen atom; Or
Two R 5Substituting group is represented the alkylidene group of 4-6 carbon atom jointly, comprises the alkylidene group of 4-6 the carbon atom that replaces with low alkyl group, as mentioned above, condition be season iodine compound contain 16-64 carbon atom.
Above-mentioned iodinated compounds is used in combination with Lewis acid, with catalysis isomerization process of the present invention.The example of inorganic lewis acid co-catalyst comprises alkali metal halide, zinc halide, tin halides (II), tin halides (IV), halogenated titanium (IV), four lower alkyl titanium oxide (IV), zirconium halide (IV), manganese halide (II), iron halide (III) or acetylacetonate iron (III).Preferred inorganic lewis acid co-catalyst comprises alkaline metal iodide, zinc iodide, zinc chloride, Tin tetraiodide (II), Tin tetraiodide (IV), titanium iodide (IV), tetramethyl titanium oxide (IV), tetrem titanium oxide (IV), four different third titanium oxide (IV), iodate zirconium (IV), manganese iodide (II), Manganous chloride tetrahydrate (II), ferric iodide (III), acetylacetonate iron (III) or their mixture.Particularly preferred inorganic lewis acid co-catalyst is the polarity iodide, titanium iodide (IV) for example, iodate zirconium (IV), especially zinc iodide and Tin tetraiodide.
The Lewis acid co-catalyst is preferably and is selected from organotin (IV) and antimony organic (V) compound, as three halo alkyl tin, dihalo dialkyl tin, halo trialkylated tin, tetra hydrocarbyl stannic compound and halo tetraalkyl antimony.
Concrete organometallic compound comprises following formula: compound:
Each R wherein 7Be selected from alkyl or substituted alkyl part separately, 5-20 cycloalkyl or the substituted cycloalkyl that carbon is former, the isocyclic aryl of 6-20 carbon atom or replacement isocyclic aryl, or the heteroaryl of 4-20 carbon atom or substituted heteroaryl until 20 carbon atoms;
Hal is a halogen atom, as chlorine, bromine or iodine, iodine preferably; And n is 1,2,3 or 4.
Concrete organometallic compound comprises two iodo dibutyl tins, iodo tributyl tin, iodo trioctylphosphine tin, the iodo triphenyltin, bromo tributyl tin, iodo tin trimethyl, three iodo butyl tin, tetrabutyl tin, tetra octyl tin, tin tetraphenyl, iodo thricyclohexyl tin, iodo three-(2-methyl-2 hydrocinnamyl) tin, the iodo tribenzyltin, two iodo tin methides, two iodo tin diphenyls, chloro triphenyltin, bromo triphenyltin and iodo tetraphenyl stibium.
Preferred organometallic compounds comprises that total carbon number is the iodate trialkylated tin (IV) of 3-30 carbon atom in the above-mentioned general formula:
Each R 7Substituting group is selected from the alkyl until 12 carbon atoms separately, the cycloalkyl of 5-7 carbon atom, benzyl, 2-methyl-2-hydrocinnamyl, phenyl or by at the most 3 be selected from low alkyl group, the phenyl that the substituting group of lower alkoxy or halogen atom replaces;
Hal is an iodine; With
N is 3.
Particularly preferred catalyst system comprises that (ⅰ) contains quaternary phosphonium iodine compound that adds up to 16-64 carbon atom and the combination that (ⅱ) has following general formula organotin iodide in the isomerization process provided by the invention:
Figure 921148240_IMG22
Each R wherein 6Substituting group is selected from the alkyl until 20 carbon atoms separately, benzyl, phenyl or by being selected from low alkyl group, the phenyl that lower alkoxy or halogen atom substituting group are replaced, each R until 3 7Substituting group respectively is selected from until the alkyl of 12 carbon atoms, benzyl, 2-methyl-2-hydrocinnamyl, phenyl or by 3 phenyl that replaced from low alkyl group, lower alkoxy or halogen atom substituting group at the most.
The iodate of catalyst system and the ratio of Lewis-acidic components can in very large range change, and for example, depend on used specific compound.Generally speaking, season iodide: acid mol ratio in Louis is 100: 1-0.02: in 1.To containing season iodide and the catalyst system of inorganic lewis acid, iodate: the Lewis acid mol ratio is preferably 100: 1-2: 1, be preferably 20: 1-5: 1.To containing season iodide and the lewis acidic catalyst system of organo-metallic, iodate: the Lewis acid mol ratio is preferably 20: 1-0.05: 1, be preferably 10: 1-0.1: 1.To preferably containing the catalyst system of phosphorus iodide and organotin iodide, the phosphorus iodide: organotin iodide mol ratio particularly preferably is 5: 1-0.2: 1.
Below be the object lesson of above-mentioned catalyst system, wherein the mol ratio of each component is defined as 1.0 moles of iodate:
(1) iodate four-dodecane ammonium (1.0 moles) and zinc iodide (0.05 mole)
(2) iodate triphen (hexyl) phosphorus (1.00 moles) and zinc iodide (0.007 mole)
(3) iodate triphen (hexyl) phosphorus (1.00 moles), iodate three-(2,4, the 6-trimethylbenzene) (hexyl) phosphorus (0.77 mole) and zinc iodide (0.015 mole)
(4) iodate four-dodecane ammonium (1.00 moles) and iodate tributyl tin (0.045 mole)
(5) iodate four-dodecane ammonium (1.00 moles) and two iodate dibutyl tins (0.05 mole)
(6) iodate four-dodecane ammonium (1.00 moles) and iodate triphenyltin (0.05 mole)
(7) iodate triphen (hexyl) phosphorus (1.00 moles) and iodate tributyl tin (0.007 mole)
(8) iodate triphen (hexyl) phosphorus (1.00 moles) and two iodate dibutyl tins (0.02 mole)
(9) iodate four-dodecane ammonium (1.00 moles) and iodate trioctylphosphine tin (0.05 mole)
(10) iodate triphen (hexyl) phosphorus (1.00 moles) and iodate trioctylphosphine tin (0.02 mole)
(11) iodate Si Ding Ji Arsenic (1.00 moles) and iodate trioctylphosphine tin (0.05 mole)
(12) iodate Si Xin Ji Arsenic (1.00 moles) and iodate trioctylphosphine tin (0.05 mole)
(13) iodate triphen (hexyl) phosphorus (1.00 moles) and iodate fentin (0.02 mole)
(14) iodate triphen (hexyl) phosphorus (1.00 moles) and iodate fentin (0.05 mole)
(15) iodate triphen (hexyl) phosphorus (1.00 moles) and iodate fentin (0.20 mole)
(16) iodate triphen (hexyl) phosphorus (1.00 moles) and iodate fentin (1.00 moles)
(17) iodate triphen (hexyl) phosphorus (1.00 moles) and iodate fentin (5.00 moles)
(18) iodate triphen (hexyl) phosphorus (1.00 moles) and iodate fentin (20.00 moles)
(19) iodate triphen (hexyl) phosphorus (1.00 moles) and iodate fentin (100.00 moles)
(20) iodate triphen (hexyl) phosphorus (1.00 moles) and iodate thricyclohexyl tin (5.00 moles)
(21) iodate triphen (hexyl) phosphorus (1.00 moles) and iodate three benzyl tin (5.00 moles)
(22) iodate four-dodecane phosphorus (1.00 moles) and iodate fentin (1.00 moles)
(23) iodate trioctylphosphine (octadecyl) phosphorus (1.00 moles) and iodate fentin (1.00 moles)
(24) iodate trioctylphosphine (octadecyl) phosphorus (1.00 moles) and trioctylphosphine tin (1.00 moles)
As mentioned above, by the contained liquid phase weight of reaction zone, catalyst system accounts for 10-95%(weight).Be preferably the 50-90% that catalyst system accounts for liquid reaction mixture weight.
After technology of the present invention begins and during the operate continuously, solvent system contains 2,5-dihydrofuran product and γ, and the mixture of the oligopolymer of δ-epoxy olefin reactant, wherein dihydrofuran: the oligopolymer weight ratio is 20: 1-1: 50.But, the weight ratio of the two is 2: 1-1: 20 is more general.Apparent to those of ordinary skill, when the processing beginning, both there be not oligopolymer not have 2 yet, 5-hydrogen furans exists.
In the course of processing owing to assemble at reaction zone nonvolatile oligopolymer arranged, must be continuously or at interval certain hour remove the interior liquid phase that partly contains oligopolymer of (removing) reaction zone from production system, to keep rational productive rate.The predetermined concentration of reaction zone inner catalyst system can be kept by infeeding as the catalyst component solution that is dissolved in the dihydrofuran of being produced.
Continuous liquid phase process of the present invention both can be gaseous state and had accessed operatedly, also can be liquid state and accessed operated.The gaseous state method of accessing of this technology may further comprise the steps:
(1) infeed γ continuously to reaction zone, δ-epoxy alkene is dissolved in the process solvent at reaction zone inner catalyst composition, and this solvent contains 2,5-dihydrofuran product and γ, the mixture of δ-epoxy olefin reactant oligopolymer; With
(2) from reaction zone, remove continuously and be rich in 2, the gas of 5-dihydrofuran product;
Wherein catalyst component contains (ⅰ) iodate and the Lewis acid that (ⅱ) is selected from inorganic lewis acid, organotin (IV) compound, organo-antimony compound or its mixture; By the gross weight of reaction zone liquid, the concentration of catalyst system is 10-95%(weight in the reaction zone liquid); The reaction zone liquidus temperature is remained on 65-160 ℃.With this kind operating method, liquid reaction mixture is kept at high temperature, contain 2 to provide, the gaseous effluent of 5-dihydrofuran product, nonvolatile catalyst component and oligopolymer process solvent are still stayed in the reaction mixture simultaneously.The concrete epoxy olefin reactant that liquid reaction mixture is remained on generate the specified temp of gaseous effluent to depend on to infeed in the reaction zone and the pressure of maintenance, generally speaking, for making 3,4-epoxy-1-butylene is isomerizated into 2,5-dihydrofuran, temperature are 65-160 ℃.Preferably 80-120 ℃.Reaction zone can remain on and suitably be below or above under the atmospheric pressure, as 0.3-4.5 crust (30-45KPa) (absolute pressure), but can obtain fabulous productive rate under environmental stress.
If only infeed γ to reaction zone, δ-epoxy olefin reactant therefrom removes gaseous effluent, general obtain 2,5-dihydrofuran product can contain about 5% or above unconverted reactant.As U.S.4,962,210 described these product mixtures can carry out the mixture of isolating tetrahydrofuran (THF) and 1-butanols to obtain available distillation method at hydrogenation in the presence of the nickel catalyzator.With γ, δ-epoxy olefin reactant changes into 2 for to greatest extent, and 5-dihydrofuran product can be with at least 50%, preferably 70-90%(weight) the condensation of reactor product effluent and be recycled to reaction zone.Circulation product effluent can make γ, and δ-epoxy olefin reactant generates 2, and the transformation efficiency of 5-dihydrofuran product is at the 98%(mole) or more than, and 2, contain weight in the 5-dihydrofuran product less than 2%() γ, δ-epoxy olefin reactant.
Liquid state accesses working method and comprises the following steps:
(1) infeeds continuously to reaction zone and contain γ, the homogeneous mixture of δ-epoxy olefin reactant and step (3) liquid phase (b);
(2) remove continuously from reaction zone and contain 2,5-dihydrofuran product, γ, the δ-oligopolymer of epoxy olefin reactant and the homogeneous liquid of catalyst component, and
(3) infeed the homogeneous liquid of step (2) continuously to the distillation zone, to obtain:
(a) be rich in 2, the gas phase of 5-dihydrofuran product; With
(b) contain γ, the δ-oligopolymer of epoxy olefin reactant and the liquid phase of catalyst component;
Wherein catalyst component contains (ⅰ) iodate and the Lewis acid that (ⅱ) is selected from inorganic lewis acid, organotin (IV) compound, organo-antimony compound or its mixture; By reaction zone liquid gross weight, the concentration of catalyst system remains on 10-95%(weight in the reaction zone liquid); The reaction zone liquidus temperature is 65-160%.
It is a small amount of 2 that step (3) liquid phase (b) generally contains, 5-dihydrofuran product.Reaction zone preferably contains some reactors of arranging according to the order of sequence, therein will at least 90%, better 98%(weight at least) γ, δ-epoxy olefin reactant changes into product.Temperature and pressure in the reaction zone remains on above-mentioned corresponding gaseous state and accesses in the scope of formula operation.
Further specify our novel process with following embodiment.The device that is used for embodiment 1 and 2 is by 1 liter of glass boiler (reactor), the condenser of glycol-cooled, and susceptor, circulation tank and product jar are formed.Reactor is furnished with heating mantles, mechanical stirrer, liquid feed pipe, temperature and takes into account the distillation tower head, from tower head steam is infeeded condenser.On Hewlett Packard 5890A gas-chromatography view, carry out gas chromatographic analysis with DB-1 fused silica capillary column (0.50mm internal diameter x15m).Process furnace heated 3 minutes down at 40 ℃, and the speed of following with 20 ℃/minute is heated to 185 ℃.Unless otherwise indicated, analytical results is listed with area percent among the embodiment.
Embodiment 1
Iodate fentin (400g) and iodate triphen (just-hexyl)-phosphorus (200g) is placed in the reactor, be heated to solid fusing (about 130 ℃).Speed with 580ml/h begins 2 then, and the 5-dihydrofuran advances in the reactor from following a jar pump, makes temperature reduce to 90 ℃.With 3,4-epoxy-1-butylene infeeds reactor again, and feed rate is 145ml/h., and keeping temperature simultaneously is about 90 ℃, infeeds (circulation) 2,5-dihydrofuran product with the speed of 580ml/h..Remove steam product stream continuously from reactor, and condensation, the liquid product of condensation flows into susceptor earlier, enters the product circulation tank again.The V-bar of product flow is 2.5g3 per hour, 4-epoxy-1-butylene and 661.3g2,5-dihydrofuran.Part does not enter the product jar from the product flow that circulation tank is recycled to reactor during process operation through overflow, just regularly gets the product flow sample in condenser, and analyzes with gas chromatograph.At 195 hours production periods, generation pure 2,5-dihydrofuran space-time yield is about 400g/L-h., the product average group that distills out from reactor become 0.6% 3,4-epoxy-1-butylene, 98.3%2, the 5-dihydrofuran, 0.2%2,3-dihydrofuran and 0.9% crotonic aldehyde.
Embodiment 2
With iodate four-just-dodecane ammonium (200g), zinc iodide (10g) and 2,5-dihydrofuran (100ml) places reactor, heated mixt to 90 ℃.Speed with 80ml/h infeeds 3 in the homogeneous phase solution that stirs, 4-epoxy-1-butylene, and the while is with the rate loop 2 of 160ml/h, 5-dihydrofuran product.Regularly from the reactor distillate, take a sample, analyze with gas phase look instrument.Consisting of of distillate is about 13%3,4-epoxy-1-butylene, 86%2,5-dihydrofuran and 1% crotonic aldehyde.
Embodiment 3
Place 100ml to be furnished with thermometer iodate fentin (10.1g) and triphen (n-hexyl) phosphorus (10.3g), magnetic stirrer, the distillation tower head is in the four neck round-bottomed flasks of heating kettle and feeder sleeve.After about 125 ℃ of following fused catalyst components, more than 30 minutes with 3,4-epoxy-3-methyl-1-butene (16.5g) pumps in the flask, reaction mixture is heated to 110-132 ℃ simultaneously.The overhead product that weighing is collected from flask is 10.7g, contains 71.9%3-methyl-2,5-dihydrofuran and 24.0%2-methyl-2 '-crotonaldehyde.
Embodiment 4
With iodate fentin (24.9g), iodate four-12 phosphorus (52.4g) and 2,5-dihydrofuran (15.9g) places 200ml to be furnished with thermopair, magnetic stirrer, the distillation tower head is in the four neck round-bottomed flasks of oily heating bath and reactant feeder sleeve.Heated mixt to 90 ℃ begins to add 3,4-epoxy-1-butylene.Temperature rises to 105 ℃ and remain under this temperature, in 38 hours operate continuously processes, infeeds 3 of 2350.1g, and 4-epoxy-1-butylene is recovered to 2235,6g distillate (rate of recovery is a 95.1%(weight)).The weight percent of distillate consists of 6.65%3,4-epoxy-1-butylene, 92.2%2,5-dihydrofuran 1.13% crotonic aldehyde.
Embodiment 5
With iodate fentin (25.0g), iodate trioctylphosphine (octadecyl) phosphorus (39.4g) and 2,5-dihydrofuran (10.0g) places 200ml to be furnished with thermopair, magnetic stirrer, the distillation tower head is in the four neck round-bottomed flasks of oily heating bath and reactant feeder sleeve.Heated mixt to 105 ℃ begins to add 3,4-epoxy-1-butylene.Be to infeed 2430.9g 3 during 105 ℃ of following operate continuouslys more than 40 hours, 4-epoxy-1-butylene also is recovered to 2368.6g distillate (rate of recovery 97.4%(weight)).The weight percent of distillate consists of 6.65%3,4-epoxy-1-butylene, 92.4%2,5-dihydrofuran and 0.96% crotonic aldehyde.
Embodiment 6
With iodate trioctylphosphine tin (30.7g), iodate trioctylphosphine (octadecyl) phosphorus (39.6g) and 2,5-dihydrofuran (9.9g) places 200ml to be furnished with thermopair, the phosphorus agitator, the distillation tower head is in the four neck round-bottomed flasks of oily heating bath and reactant feeder sleeve.With mixture heating up to 105 ℃, begin to add 3,4-epoxy-1-butylene.Be to infeed 1400.5g3 in 105 ℃ of following operate continuously processes more than 51 hours, 4-epoxy-1 butylene is recovered to 1336.9g distillate (rate of recovery is a 95.5%(weight)).The weight percent of distillate consists of 8.32%3,4-epoxy-1-butylene, 90.9%2,5-dioxy furans and 0.79% crotonic aldehyde.
Embodiment 7
3,4-epoxy-1-butylene forms 2, and the isomerization reaction of 5-dihydrofuran divides two sections successive reactive systems to carry out.Wherein by second reactor distillage from effluent, and with catalyst recirculation to the first reactor.Each reactor is by being furnished with heating mantles, and magnetic stirrer, thermometer, condenser, inlet and liquid access one liter of glass boiler of pipe and form.Make liquid reaction mixture from first reactor overflow to the second reactor, keep the liquid level in first reactor to be about 500ml simultaneously.The liquid that accesses from second reactor is received vacuum distillation plant with magnetic valve.Control magnetic valve with liquid level sensing device, make effluent flow in the distillation tower with opening magnetic valve in second reactor, removing product and any unreacted raw material, thereby the regulator solution position sensing device is to keep the position at 250-500ml.
The end jar of water distilling apparatus is furnished with heating mantles and the side accesses mouth.From the effusive effluent of jar sent to pump inlet in case with catalyst recirculation to first reactor.All transfer limes are heated and are adiabatic, therefore can maintain the temperature at about 90 ℃.Reaction system is cleared up with the catalyst mixture of fusing, and catalyst mixture is by roughly the iodate fentin and iodate trioctylphosphine (octadecyl) phosphorus of equimolar amount are formed.Is 90-95 ℃ with the reactor heating to keep temperature.
Open the catalyst recirculation pump, infeed catalyzer to first reactor inlet with the speed of 1000-2000ml/h.Operating period, the amount of the catalyst component that contains of reactor was about 400g iodate trioctylphosphine (octadecyl) phosphorus and 255g iodate fentin.The bed of the 3A molecular sieve by 300ml infeeds 3 to first reactor, 4-epoxy-1-butylene with the speed of about 120ml/h.Make reaction mixture flow through two reactors, arrive in the distillation tower remain under 280-305 holder (torr) and about 90 ℃.The distillatory product is collected in the refrigerative receptor, makes remainder catalyst flow into recycle pump to get back in the reactor from pot bottom.Constantly form the small amounts of oligomer byproduct between the reaction period.A certain amount of this part material is allowed in the reaction mixture, to increase the 25-35%(weight of total amount) liquid level.During beginning, the inventory of second reactor is maintained at about 250ml, and along with the increase of oligopolymer amount, material rises to about 500ml.Group of products becomes 0.3% epoxy butylene, 98.7% dihydrofuran and 1.0% crotonic aldehyde.
Below specifically describe in detail, be to be understood that within the spirit and scope of the present invention and can carry out multiple changes and improvements with reference to the preferred embodiment of the present invention.

Claims (17)

1, be used to process and contain 2 of 4-8 carbon atom, the continuous processing of 5-dihydrofuran comprises step:
(1) in the reaction zone that contains the solution of forming by following ingredients, infeed γ continuously, δ-epoxy alkene:
(A) catalyst system of catalytic amount comprises (i) iodate and (ii) is selected from the Lewis acid of inorganic lewis acid, organotin (IV) compound, organo-antimony compound or their mixture; With
(B) process solvent system contains 2,5-dihydrofuran product and γ, the oligopolymer of δ-epoxy olefin reactant; With
(2) from reaction zone solution, remove continuously and contain 2, the steam of 5-dihydrofuran; Wherein, the liquid phase of reaction zone being maintained under 65-160 ℃, is 10-95% weight by the concentration of catalyst system in the reaction zone liquid.
2, be used to process according to claim 1 and contain 2 of 4-8 carbon atom, the technology of 5-dihydrofuran comprises step:
(1) infeed γ continuously to reaction zone, δ-epoxy alkene is dissolved in catalyst component in reaction zone and contains 2, and 5-dihydrofuran product and γ are in the process solvent of δ-epoxy olefin reactant; With
(2) remove continuously from reaction zone and be rich in 2,5-dihydrofuran product; Wherein catalyst component comprises that (ⅰ) iodate (ⅱ) is selected from the Lewis acid of inorganic lewis acid, organotin (IV) compound, organo-antimony compound or their mixture; The concentration of catalyst system remains on 10-95% weight in the reaction zone liquid, by the gross weight of reaction zone liquid; And the liquidus temperature of reaction zone remained under 65-160 ℃.
3, according to the technology of claim 2, wherein 2,5-dihydrofuran and γ, δ-epoxy alkene has structural formula
Figure 921148240_IMG1
Wherein every R 1Respectively be selected from hydrogen and methyl.
4, according to the technology of claim 3, wherein process under 80-120 ℃ of temperature, pressure is 0.3-4.5 crust (30-450KPa) absolute pressure, is no more than 4 R 1Substituting group is expressed as methyl.
5, be used to process and contain 2 of the former and following structural of 4-8 carbon, the continuous processing of 5-dihydrofuran,
Comprise step:
(1) infeeds the γ of following formula continuously to the reaction zone that contains the solution of forming by following ingredients, δ-epoxy alkene;
Figure 921148240_IMG3
(A) catalyst system of catalytic amount contains (ⅰ) iodate and (ⅱ) organotin (IV) compound; With
(B) 2,5-dihydrofuran product and γ, the mixture of the oligopolymer of δ-epoxy olefin reactant; With
(2) from reaction zone solution, remove continuously and contain 2, the steam of 5-dihydrofuran; Wherein keep the liquidus temperature of reaction zone to remain under 65-160 ℃, by the gross weight of reaction zone liquid, the concentration of catalyst system is 50-90% weight in the reaction zone liquid, each R 1Substituting group respectively is selected from hydrogen and methyl.
6, according to the technology of claim 5, wherein iodate is selected from the compound of following structural:
Figure 921148240_IMG4
Each R wherein 5Substituting group is selected from the alkyl until 20 carbon atoms separately, each R 6Substituting group is selected from R separately 5, benzyl, phenyl or by at the most 3 be selected from low alkyl group, the phenyl that lower alkoxy or halogen atom substituting group replace; Perhaps
Two R 5Substituting group is represented the alkylidene group of 4-6 carbon atom jointly, comprises the alkylidene group of 4-6 the carbon atom that replaces with low alkyl group; Condition be season iodine compound contain 10-64 carbon atom; With
Lewis acid is selected from zinc iodide or Tin tetraiodide (II).
7, according to the technology of claim 5, wherein iodate is selected from the compound of following formula:
Figure 921148240_IMG5
Each R wherein 5Substituting group respectively is selected from the alkyl until 20 carbon atoms, each R 6Substituting group is selected from R 5, benzyl, phenyl or by at the most 3 be selected from low alkyl group, the phenyl that the substituting group of lower alkoxy or halogen atom replaces; Perhaps
Two R 5Substituting group is represented the alkylidene group of 4-6 carbon atom jointly, comprises the alkylidene group of 4-6 the carbon atom that replaces with low alkyl group, condition be season iodine compound contain 16-64 carbon atom; With
Lewis acid is selected from organotin (IV) and has antimony organic (V) compound of following formula:
Wherein
Each R 7Respectively be selected from alkyl or substituted alkyl part, the cycloalkyl or the substituted cycloalkyl of 5-20 carbon atom arranged, the isocyclic aryl of 6-20 carbon atom is arranged or replace isocyclic aryl, or the heteroaryl or the substituted heteroaryl of 4-20 carbon atom are arranged until 20 carbon atoms;
Hal is a halogen atom; With
N is 1,2,3 and 4.
8, according to the technology of claim 5, wherein iodate is selected to contain and adds up to 10-60 carbon atom, has the season iodate phosphorus compound of following formula:
Figure 921148240_IMG6
Lewis acid is selected from the iodate organo-tin compound of following formula:
Each R wherein 6Substituting group respectively is selected from the alkyl until 20 carbon atoms, benzyl, phenyl or by 3 phenyl that the substituting group that is selected from low alkyl group, lower alkoxy or halogen atom replaces at the most, each R 7Substituting group respectively is selected from the alkyl until 12 carbon atoms, benzyl, 2-methyl-2-hydrocinnamyl, phenyl or by being selected from low alkyl group until 3, the phenyl that lower alkoxy or halogen atom substituting group replace; With
Season iodate phosphorus: the mol ratio of iodate organotin is 10: 1-0.1: 1.
9, be used to process 2, the continuous processing of 5-dihydrofuran comprises step:
(1) infeed 3 continuously to the reaction zone that contains the solution of forming by following ingredients, 4-epoxy-1-butylene:
(A) catalyst system of catalytic amount comprises (ⅰ) season iodate phosphorus, and its total carbon atom is 16-60 comparatively, and structural formula is
Figure 921148240_IMG7
(ⅱ) organotin (IV) compound of following formula is arranged:
Each R wherein 6Substituting group respectively is selected from the alkyl until 20 carbon atoms, benzyl, phenyl or by 3 phenyl that the substituting group that is selected from low alkyl group, lower alkoxy or halogen atom replaces at the most, each R 7Substituting group respectively is selected from the alkyl until 12 carbon atoms, benzyl, 2-methyl-2-hydrocinnamyl, phenyl or by 3 phenyl that the substituting group that is selected from low alkyl group, lower alkoxy or halogen atom replaces at the most; And mol ratio (ⅰ): be 10 (ⅱ): 1-0.1: 1; With
(B) 2,5-dihydrofuran and 3, the mixture of 4-epoxy-1-butylene; With
(2) remove continuously from reaction zone and contain 2, the steam of 5-dihydrofuran; Wherein, the liquidus temperature of reaction zone is remained under 80-120 ℃, the concentration of catalyst system remains on 50-90% weight in the reaction zone liquid, by the gross weight of reaction zone liquid.
10, according to being used to process and containing 2 of 4-8 carbon atom of claim 1, the technology of 5-dihydrofuran comprises step:
(1) infeed continuously and contain γ, δ-epoxy olefin reactant and step (3) liquid phase (b) are to reaction zone;
(2) remove continuously from reaction zone and contain 2,5-dihydrofuran product, γ, the oligopolymer of δ-epoxy olefin reactant and the homogeneous liquid of catalyzer composition and
(3) homogeneous liquid that infeeds step (2) continuously to the distillation zone is to obtain:
(a) be rich in 2, the vapor phase of 5-dihydrofuran product: and
(b) contain γ, the oligopolymer of δ-epoxy olefin reactant and the liquid phase of catalyzer composition;
Wherein, the catalyzer composition contains (ⅰ) iodate and (ⅱ) is selected from the Lewis acid of inorganic lewis acid, organotin (IV) compound, organo-antimony compound or their mixture:, remain on 10-95% weight in the reaction zone liquid in the concentration of catalyst system by the gross weight of reaction zone liquid; Remain on 65-160 ℃ with the liquidus temperature of reaction zone.
11, according to the technology of claim 10, wherein, 2,5-dihydrofuran and γ, δ-epoxy alkene has following structural:
Wherein, each R 1Respectively be selected from hydrogen and methyl.
12, according to the technology of claim 11, wherein this technology is to be that 80-120 ℃ and pressure are to carry out no more than 4 R under 0.3-4.5 crust (30-450KPa) absolute pressure in temperature 1Substituting group is represented methyl.
13, be used to process and contain 2 of 4-8 carbon atom and following formula, the continuous processing of 5-dihydro furan spray,
Figure 921148240_IMG9
Comprise step:
(1) infeeds the γ that comprises following formula continuously, δ-epoxy alkene
Figure 921148240_IMG10
And the homogeneous mixture of step (3) liquid phase (b) is to reaction zone;
(2) remove continuously from reaction zone and contain 2 of following formula, 5-dihydrofuran product, γ, the δ-oligopolymer of epoxy alkane reactant and the homogeneous liquid of catalyst component
Figure 921148240_IMG11
(3) homogeneous liquid that infeeds step (2) continuously to the distillation zone is to obtain:
(a) be rich in 2, the vapor phase of 5-dihydrofuran product; With
(b) contain 2,5-dihydrofuran product, γ, the δ-oligopolymer of epoxy olefin reactant and the liquid phase of catalyst component;
Wherein, catalyst component contains (ⅰ) iodate and (ⅱ) is selected from the Lewis acid of inorganic lewis acid, organotin (IV) compound, organo-antimony compound or their mixture; By reaction zone liquid gross weight, the concentration of catalyst system remains on 10-95% weight in the reaction zone liquid; Remain on 65-160 ℃ with the liquidus temperature of reaction zone.
14, according to the technology of claim 13, wherein, iodate is selected from following formula: compound
Wherein, each R 5Substituting group respectively is selected from the alkyl until 20 carbon atoms, each R 6Substituting group respectively is selected from R 5, benzyl, benzyl or by 3 phenyl that the substituting group that is selected from low alkyl group, lower alkoxy or halogen atom replaces at the most; Or
Two R 5Substituting group represents that jointly the alkylidene group of 4-6 carbon atom comprises the alkylidene group of 4-6 the carbon atom that replaces with low alkyl group, condition be season iodide to contain 16-64 carbon former; With
Lewis acid is selected from zinc iodide or Tin tetraiodide (II).
15, according to the technology of claim 13, wherein, iodate is selected from following formula: compound
Figure 921148240_IMG13
Wherein, each R 5Substituting group respectively is selected from the alkyl until 20 carbon atoms, each R 6Substituting group respectively is selected from R 5, benzyl, phenyl or by 3 phenyl that the substituting group that is selected from low alkyl group, lower alkoxy or halogen atom replaces at the most; Or
Two R 5Substituting group is jointly represented the alkylidene group of 4-6 carbon atom, comprises the alkylidene group of 4-6 the carbon atom that replaces with low alkyl group, condition be season iodide contain 16-64 carbon atom; With
Lewis acid is selected from the organotin (IV) and antimony organic (V) compound of following formula
Wherein:
Each R 7Respectively be selected from alkyl or substituted alkyl part until 20 carbon atoms, or the cycloalkyl or the substituted cycloalkyl of 5-20 carbon atom are arranged, or the isocyclic aryl of isocyclic aryl that 6-20 carbon atom replace or replacement is arranged or the heteroaryl or the substituted heteroaryl part of 4-20 carbon atom are arranged;
Hal is a halogen atom; With
N 1,2, and 3 or 4.
16, according to the technology of claim 13, wherein, iodate is selected from the compound of the season iodate phosphorus that contains 16-60 carbon atom and following formula:
Figure 921148240_IMG14
Be selected from the iodate organo-tin compound of following formula with Lewis acid:
Wherein, each R 6Substituting group respectively is selected from the alkyl until 20 carbon atoms, benzyl, phenyl or by being selected from the phenyl that low alkyl group, lower alkoxy or halogen atom substituting group replace, each R until 3 7Substituting group respectively is selected from the alkyl until 12 carbon atoms, benzyl, 2-methyl-2-hydrocinnamyl, phenyl or by being selected from the phenyl that low alkyl group, lower alkoxy or halogen atom substituting group replace until 3; With
The mol ratio of season iodate phosphorus and iodate organotin is 10: 1-0.1: 1.
17, be used to process 2, the technology of 5-dihydrofuran comprises step:
(1) infeeds continuously to reaction zone and contain 3, the homogeneous mixture of 4-epoxy-1-butylene and step (3) liquid phase (b);
(2) remove continuously from reaction zone and contain 2,5-dihydrofuran product, 3, the homogeneous liquid of 4-epoxy-1-butylene and catalyst component; With
(3) infeed the homogeneous liquid of step (2) continuously to the distillation zone, to obtain
(a) be rich in 2, the vapor phase of 5-dihydrofuran; With
(b) contain 2,5-dihydrofuran product, 3, the liquid phase of 4-epoxy-1-butylene and catalyst component;
Wherein catalyst component contains the season iodate phosphorus that (ⅰ) contains a total 16-60 carbon atom and following formula:
Figure 921148240_IMG15
(ⅱ) organotin (IV) compound of following formula is arranged:
Wherein, each R 6Substituting group respectively is selected from the alkyl until 20 carbon atoms, benzyl, phenyl or by at the most 3 be selected from the phenyl that low alkyl group, lower alkoxy or halogen atom substituting group replace; Each R 7Substituting group respectively is selected from the alkyl until 12 carbon atoms, benzyl, 2-methyl-2-hydrocinnamyl, phenyl or by at the most 3 be selected from the phenyl that low alkyl group, lower alkoxy or halogen atom substituting group replace; (ⅰ): mol ratio (ⅱ) is 10: 1-0.1: 1; Catalyst system concentration in the reaction zone liquid remains on 50-95% weight, and by the gross weight of reaction zone liquid, the liquidus temperature of reaction zone remains on 80-120 ℃.
CN92114824A 1991-11-19 1992-11-19 Continuous process for the manufacture of 2,5-dihydrofurans from gamma, delta-epoxybutenes Expired - Fee Related CN1050837C (en)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US74840891A 1991-11-19 1991-11-19
US748,408 1991-11-19
US07/962,545 US5315019A (en) 1991-11-19 1992-10-19 Continuous process for the manufacture of 2,5-dihydrofurans from γ, δ-epoxybutenes
US962,545 1992-10-19

Publications (2)

Publication Number Publication Date
CN1073435A true CN1073435A (en) 1993-06-23
CN1050837C CN1050837C (en) 2000-03-29

Family

ID=27114936

Family Applications (1)

Application Number Title Priority Date Filing Date
CN92114824A Expired - Fee Related CN1050837C (en) 1991-11-19 1992-11-19 Continuous process for the manufacture of 2,5-dihydrofurans from gamma, delta-epoxybutenes

Country Status (16)

Country Link
US (1) US5315019A (en)
EP (1) EP0624157B1 (en)
JP (1) JP3184527B2 (en)
KR (1) KR100222119B1 (en)
CN (1) CN1050837C (en)
AT (1) ATE149492T1 (en)
AU (1) AU665502B2 (en)
BR (1) BR9206778A (en)
CA (1) CA2122455C (en)
DE (1) DE69217999T2 (en)
DK (1) DK0624157T3 (en)
ES (1) ES2098562T3 (en)
GR (1) GR3022904T3 (en)
MY (1) MY108257A (en)
TW (1) TW275627B (en)
WO (1) WO1993010111A1 (en)

Families Citing this family (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1995019382A1 (en) * 1994-01-18 1995-07-20 Eastman Chemical Company Polyether polymers derived from 3,4-epoxy-1-butene
DE4422671A1 (en) 1994-06-30 1996-01-04 Basf Ag Process for the preparation of 2,5-dihydrofuran
DE4424219A1 (en) * 1994-07-09 1996-01-11 Basf Ag Process for the preparation of 2,5-dihydrofuran
US5466832A (en) * 1995-02-13 1995-11-14 Eastman Chemical Company Process for the manufacture of 2,5-dihydrofurans from γ, δ-epoxybutenes
US5591874A (en) * 1995-09-29 1997-01-07 Eastman Chemical Company Process for the preparation of 2,5-dihydrofuran compounds
DE19539331A1 (en) * 1995-10-23 1997-04-24 Basf Ag Process for the separation of oligomeric by-products from an isomerization catalyst
US5681969A (en) * 1996-05-03 1997-10-28 Eastman Chemical Company Continuous process for the conversion of 2,5-dihydrofuran to 2,3-dihydrofuran
US5693833A (en) * 1996-08-26 1997-12-02 Eastman Chemical Company Process for the reactivation of iodine-containing catalysts
JP2001512522A (en) * 1997-02-25 2001-08-21 イーストマン ケミカル カンパニー Polymers containing functionalized olefin monomers
US6335455B1 (en) * 1998-01-12 2002-01-01 Eastman Chemical Company Process for the production of 2,5-dihydrofuran
US5986141A (en) * 1998-09-29 1999-11-16 Eastman Chemical Company Process for the production of cyclopropanemethylamine
US6608156B1 (en) 2000-10-05 2003-08-19 Eastman Chemical Company Process for preparing interpolymers of ethylene and 2,3-dihydrofuran, or a heteroatom substituted olefin monomer and ethylene interpolymers
US6472491B1 (en) 2000-10-05 2002-10-29 Eastman Chemical Company Process for preparing ethylene interpolymers and ethylene interpolymers
US6353140B1 (en) 2000-10-19 2002-03-05 Eastman Chemical Company Process for the purification of cyclopropanecarboxaldehyde
US7001369B2 (en) * 2003-03-27 2006-02-21 Scimed Life Systems, Inc. Medical device
CN101448807B (en) * 2006-03-17 2013-02-06 康奈尔大学 Production of 2,5-dihydrofurans and analogous compounds

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3812158A (en) * 1970-12-17 1974-05-21 Petro Tex Chem Corp Preparation of dihydrofuran from 3,4-epoxy-1-butene,3,4-dihydroxy-1-butene,or 1,4-dihydroxy-2-butene
US3932468A (en) * 1974-02-08 1976-01-13 Chevron Research Company Dihydrofuran preparation
US3996248A (en) * 1975-11-17 1976-12-07 Chevron Research Company Preparation of 2,5-dihydrofurans from butadiene monoxides
DE3926147A1 (en) * 1989-08-08 1991-02-14 Basf Ag METHOD FOR PRODUCING 2,5-DIHYDROFURANES
US5082956A (en) * 1990-03-08 1992-01-21 Eastman Kodak Company Isomerization of epoxyalkenes to 2,5-dihydrofurans

Also Published As

Publication number Publication date
CA2122455A1 (en) 1993-05-27
AU665502B2 (en) 1996-01-04
ES2098562T3 (en) 1997-05-01
CA2122455C (en) 1997-12-09
DK0624157T3 (en) 1997-09-15
KR100222119B1 (en) 1999-10-01
JPH07507043A (en) 1995-08-03
AU3131693A (en) 1993-06-15
TW275627B (en) 1996-05-11
DE69217999D1 (en) 1997-04-10
GR3022904T3 (en) 1997-06-30
ATE149492T1 (en) 1997-03-15
BR9206778A (en) 1995-11-07
JP3184527B2 (en) 2001-07-09
CN1050837C (en) 2000-03-29
EP0624157B1 (en) 1997-03-05
EP0624157A1 (en) 1994-11-17
WO1993010111A1 (en) 1993-05-27
DE69217999T2 (en) 1997-06-12
MY108257A (en) 1996-08-30
US5315019A (en) 1994-05-24

Similar Documents

Publication Publication Date Title
CN1050837C (en) Continuous process for the manufacture of 2,5-dihydrofurans from gamma, delta-epoxybutenes
JP3070765B2 (en) Isomerization of epoxy alkenes to 2,5-dihydrofuran and catalyst compositions useful therefor
KR100899058B1 (en) Process for making dialkyl carbonates
CN1863754A (en) Process for the synthesis of unsaturated alcohols
CN1083411C (en) Preparation of propene
CN1027259C (en) Improved process for preparation of 3,5,6-trichloropyridin-2-01
CN1874987A (en) Method for producing ester condensed product
JPH08500283A (en) Method for separating oligomeric material from catalyst mixture
JP4042870B2 (en) Process for continuous production of aromatic carbonates
CN110894185B (en) Preparation method of diphenyl carbonate compound
CN110894204A (en) Catalyst for preparing diphenyl carbonate compound and preparation method and application thereof
US6201138B1 (en) Isomerization of epoxyalkenes to 2,5-dihydrofurans
EP1049688B1 (en) Process for the production of 2,5-dihydrofuran
CN1434814A (en) Gas phase epoxidation of non-allylic olefins
KR0179735B1 (en) Method of preparing dimethyldichlorosilane
CN116041182A (en) Preparation method of diphenyl carbonate compound
CN113666806A (en) Preparation method of bisphenol F2, 3-dihydroxypropyl (2-chloro-1-propyl) ethyl ether
JPH0578284A (en) Production of dialkyl carbonate
KR20060136454A (en) Process for preparing dialkyl carbonate

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C53 Correction of patent of invention or patent application
CB02 Change of applicant information

Applicant after: Eastman Chem Co.

Applicant before: Eastman Kodak Co.

COR Change of bibliographic data

Free format text: CORRECT: APPLICANT; FROM: EASTMAN KODAK CO. TO: YISIMAN CHEMICAL COMPANY

C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
C15 Extension of patent right duration from 15 to 20 years for appl. with date before 31.12.1992 and still valid on 11.12.2001 (patent law change 1993)
OR01 Other related matters
C19 Lapse of patent right due to non-payment of the annual fee
CF01 Termination of patent right due to non-payment of annual fee